ES2671929T3 - Methods of sampling non-atmospheric vessels in a parallel reactor system - Google Patents

Abstract

A method for sampling from a non-atmospheric reaction vessel of a parallel reactor system, the reactor system includes a reactor assembly comprising at least two reaction vessels, antechambers arranged above each reaction vessel, antechamber sealing elements , a port valve arranged between each antechamber and each reaction vessel and a sampling system for sampling material from the reaction vessels, the sampling system comprises a sampling pump, a sampling needle has a tip and a sampling valve disposed between the sampling pump and the tip, the method comprises: lowering the sampling needle into an antechamber to form a substantially fluid tight seal between the antechamber sealing member and the sampling needle; Lower the sampling needle into the reaction vessel, the vessel has reactor material in it; introducing material from the reaction vessel into the sampling needle to form a sample fuel rod; lift the sampling needle to position the tip of the sampling needle in the antechamber; close the port valve after placing the tip of the sampling needle in the antechamber; retracting the bar so that a first portion is provided between the sampling valve and the sampling pump and a second portion is provided between the sampling valve and the tip of the sampling needle; and discharging the bar onto a target substrate.

Description

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DESCRIPTION

Sampling methods of non-atmospheric vessels in a parallel reactor system Cross reference to related request

This application claims the benefit of U.S. Provisional Application No. 61 / 817,670, filed on April 30, 2013.

Disclosure Field

The field of disclosure relates to methods for sampling reactor contents in parallel reactor systems and, in particular embodiments, for sampling reactor contents in pressurized reaction vessels.

Background

Research and development programs aimed at the discovery of materials use high-performance selection tools to evaluate multiple different candidate materials and / or process conditions to reduce the costs and time associated with the identification of promising candidate materials and / or conditions of the process. process. Various high-performance parallel reactor systems have been developed to evaluate multiple candidate materials and / or process conditions by performing multiple reactions in parallel (i.e., during the same time period or overlapping time period).

There is a continuing need for methods to sample the contents of the reaction vessel in parallel reactor systems that are capable of sampling when the contents of the reaction vessels are pressurized. Examples of prior art technology are shown in documents US2003 / 0211016, US2008 / 0286171 and US2003 / 0152489.

Summary

One aspect of the present disclosure relates to a method for sampling a non-atmospheric reaction vessel from a parallel reactor system. The reactor system includes a reactor matrix comprising at least two reaction vessels, antechambers disposed above each reaction vessel, antechamber sealing elements, a port valve disposed between each antechamber and each reaction vessel and a system of sampling to sample the material of the reaction vessels. The sampling system includes a sampling pump, a sampling needle that has a tip and a sampling valve disposed between the sampling pump and the tip. The sampling needle is lowered into a antechamber to form a substantially fluid tight seal between the sealing element of the anteroom and the sampling needle. The sampling needle is lowered into the reaction vessel that has reactor material inside. The material from the reaction vessel is introduced into the sampling needle to form a sample bar. The sampling needle is raised to place the tip of the sampling needle in the antechamber. The port valve closes after placing the tip of the sampling needle in the antechamber. The bar is retracted so that a first portion is disposed between the sampling valve and the sampling pump and a second portion is disposed between the sampling valve and the tip of the sampling needle. The bar is unloaded on a target substrate.

There are various refinements of the characteristics indicated in relation to the aspects of the present disclosure mentioned above. Additional features may also be incorporated in the aforementioned aspects of the present disclosure. These refinements and additional features may exist individually or in any combination. For example, several features discussed below in relation to any of the illustrated embodiments of the present disclosure may be incorporated into any of the aspects of the present description described above, alone or in any combination.

Brief description of the drawings

Figure 1 is a perspective view of a reactor system inside a glove box;

Figure 2 is a front view of a reactor matrix and distribution system;

Figures 3-4 are front views of a reaction vessel of the assembly of Figure 2;

Figure 5 is a front view of the top plate assembly of the assembly showing a sealing element, antechamber and access valve before insertion of an injection needle;

Figure 6 is a front view of the matrix top plate assembly showing a sealing element, an antechamber and a port valve after insertion of the injection needle into the antechamber;

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Figure 7 is a front view of the top plate assembly of the assembly showing a sealing element, an antechamber and a port valve after insertion of the injection needle through the open port valve;

Figure 8 is a front view of three alternative sealing elements for sealing an antechamber;

Figure 9 is a perspective view of a reactor matrix and injection matrix;

Figure 10 is a perspective view of the reactor matrix of Figure 9;

Figure 11 is a front view of a reaction vessel of the reactor assembly of Figure 9;

Figure 12 is a front view of a dispensing system for injecting fluid into the reaction vessels;

Figure 13 is a perspective view of a cross section of a sealing element of a waste container before insertion of an injection needle;

Figure 14 is a perspective view of a cross section of a sealing element of a waste container after the formation of a seal between the injection needle and an O-ring and before the opening of the port valve;

Figure 15 is a perspective view of a cross-section of a sealing element of the waste container after the access valve is opened and the injection needle is fully positioned to deliver the waste.

Figure 16 is a front view of a top plate assembly for sampling reaction vessels and a sampling assembly before insertion of a sampling needle;

Figure 17 is a front view of an upper plate assembly for sampling reaction vessels and a sampling assembly after insertion of the sampling needle into the antechamber; Y

Figure 18 is a front view of a top plate assembly for sampling reaction vessels and a sampling assembly after insertion of the sampling needle through the open port valve.

The corresponding reference characters indicate corresponding parts throughout the drawings.

Detailed description

Referring now to Figure 1, an embodiment of an automatic parallel reactor system is generally designated as 10. The parallel reactor system 10 (also referred to herein simply as "reactor system") includes reactor components such as an assembly 20 of a parallel reactor within a housing 8 which is commonly referred to in the art as a "glove box". The housing 8 of this embodiment is substantially air tight in relation to the surrounding environment. In other embodiments, the parallel reactor system does not include a glove box (for example, a housing containing reactor components such as a reactor matrix) and it is contemplated that sampling according to this disclosure may take place outside a box of gloves.

In embodiments in which the reactor system includes a glove box, a gas (for example, inert gas such as nitrogen or argon, or alternatively a reactive gas, including without limitation hydrogen used in hydrogenation reactions) can be introduced into The parallel reactor system. The gas can be continuously introduced into an inlet and continuously withdrawn through an outlet (not shown). The housing 8 may be pressurized to prevent ambient gases from entering the housing. In embodiments in which inert gas is used, the inert gas can be treated to remove potential contaminants (water vapor and / or oxygen), for example, by treating the gases in a washing device.

The reactor system 10 has three sections: a first section 18, a second section (also referred to herein as the main chamber) 19 and a third section 22. The second section 19 of the housing 8 includes most of the components of the reactor system including reactor matrices, reagents, robotic arms and the like. The first section 18 and the third section 22 provide additional workspace for the user and may contain auxiliary components. The first section 18 and the third section 22 may contain reactor components such as trays and individual reagent vessels, reactor components such as coating vials (ie, test tubes) and impellers. Such components can be added or removed by the use of antechambers 31, 33 which can be isolated from the first section 18 and the third section 22. The components can then be added to the antechamber (or removed from the antechamber if system components 10 are being removed). ) by purging the antechambers 31, 33 with inert gas (i.e. at least one vacuum cycle and washing with inert gas) and the pressure

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It is equivocal with the first and third sections 18, 22 of the reactor system. The antechambers 31, 33 can then be opened to the second and third sections 18, 22 to add material to the reaction system 10. The reactor system 10 may have less than three sections and, in some embodiments, has only one section that contains all the components of the reactor system (ie, the first section 18 and / or the third section 22 are optional).

The introduction of inert gases into and out of the housing 8 may allow the amount of water vapor in the system 10 to be reduced to less than about 10 ppm or even less than about 1 ppm. The use of inert gas can also allow the amount of oxygen in the system to be reduced to less than about 10 ppm or even less than about 1 ppm. However, the reactor system may include more or less water vapor and oxygen without departing from the scope of the present disclosure. The concentrations of oxygen and water in the inert gas can be measured and, as in some embodiments, are measured semi-continuously or continuously.

Referring now to Figure 2, a reactor matrix 20 of the reactor system is shown. The array 20 of reactors allows automated control (and, optionally, individual control) of temperature, pressure and stirring so that the optimization of the material (eg, catalyst) can be performed. The matrix 20 may be housed in the main chamber 19 of the housing 8. The reactor matrix 20 includes a number of reaction vessels 9 within a reaction block 11 and a top plate assembly 13 that seals the reaction vessels.

Matrix 20 shown in Figure 2 includes eight reaction vessels 9 in a 1x8 arrangement. The matrix 20 may include two reaction vessels 9 or more, as in other embodiments, approximately 4 reaction vessels or more, approximately 8 reaction vessels or more, approximately 16 reaction vessels or more or even approximately 48 reaction vessels or more . The reaction vessels may be in any suitable arrangement (for example, 1x8, 2x4, 4x4, etc.).

Although the reaction vessels 9 are generally shown in the Figures as reaction vials, it should be understood that other vessels (eg, wells including microtiter plate wells and the like) can be used without departing from the scope of the present disclosure.

The reactor matrix 20 includes an injection matrix 85 (Figure 9) that includes access ports 87 and valves that are used to isolate the contents of the reaction vessels 9 during material delivery and sampling of the reaction mixture.

Referring now to Figure 10 (the injection matrix is omitted), the reactor matrix includes a heated reactor block 91 and a cooling fluid inlet 92 (eg gas or liquid) and a cooling fluid outlet 93 . In some embodiments, the liquid is used as a cooling fluid for maximum heat transfer. A fluid distribution manifold 79 (Figure 11) directs the cooling fluid around the individual reaction vessels 9 so that the temperature within each reaction vessel can be controlled below room temperature. In one embodiment, the flow of cooling fluid (ie, the temperature gradient between the cooling fluid and the contents of the reaction vessel) to individual reactors can be controlled for a maximum thermal response.

The reactor matrix 20 includes a process gas inlet 82 (i.e., inlet of reactive gas or inert gas) and outlet 97 for the automatic introduction of a process gas that pressurizes each reaction vessel 9 and provides the environment for each container. Each reaction vessel includes a pressure sensor 99 for measuring and transmitting the pressure in each reaction vessel.

The matrix includes cooling channels 30 (Figure 3) and cooling inputs 27 (Figure 11) and cooling outputs 29 associated with each reaction vessel 9. The matrix also includes heated zones 32 (Figure 3) in thermal communication with each reaction vessel 9 to control the temperature of the reaction mixture in the vessel. The heated zones 32 can be heated by the use of a bar heater 90 (Figure 11). An external thermocouple can be used (not shown, but its position indicated by "79") to indirectly measure the temperature of the reaction contents. The assembly may include insulation to help regulate the temperature of the reaction mixture.

An automatic dispensing system 15 (Figure 2) is used to supply material in each reaction vessel 9. The dispensing system 15 is controlled by an arm (not shown) that places the dispensing system on each reaction vessel 9 to deliver material.

Referring now to Figure 3, the contents of the reaction vessels 9 can be agitated by the use of a magnetic unit 6 that rotates a magnetically coupled agitator 21. The stirrer 21 may include a impeller 24 to promote agitation of the contents of the reaction vessel 9. The rotation of the magnet 6 causes a corresponding magnet in the reaction vessel to rotate together with an agitator 21 attached to the magnet thereby agitating the contents of the reaction vessel 9. In some embodiments and as shown in Figure 3, the stirrer 21 extends from an upper end 25 of the reaction vessel 9 and does not come into contact with the walls of the reaction vessel during use.

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The reactor arrangement may include an immersion tube 12 (Figure 4) with a frit 14 in each reaction vessel 9 to remove fluids from the reaction vessel 9. The frit 14 acts to filter solids while removing fluid from the container 9. The frit 14 can be periodically washed to prevent excess solid material from clogging the frit 14.

A second tube 16 can be used for solvent injection. In some embodiments, the tube 16 is removed and the solvent is introduced through the immersion tube thereby washing the frit 14.

In some embodiments and as shown in Figures 3-7, the parallel reactor system includes a sealing element 3 disposed above each reaction vessel 9. The sealing element 3 forms a substantially fluid-tight seal between an injection needle 50 of the system dispenser 15 (Figure 2).

Alternative sealing elements 3 suitable for covering an opening within the upper plate assembly 13 on the reaction vessel 9 are shown in Figure 8. A first embodiment of the sealing element 3 is mentioned as 3a in Figure 8. The sealing element 3a is a septum. To supply material in the reaction vessel 9, the injection needle 50 (Figure 2) is lowered and the septum 3a pierced. Sept 3a forms a seal around the injection needle and insulates the reaction vessel from the other components of the parallel reactor system. The injection needle continues to lower to supply material as described below.

A second embodiment of the sealing element 3 is referred to as 3b in Figure 8. The upper plate assembly 13 may include duckbill injectors 3b that are seated in the openings within the upper plate assembly. To supply material in the reaction vessel 9, the injection needle is lowered and the duckbill injector 3b is perforated. The duckbill injector 3b forms a seal around the injection needle and isolates the reaction vessel from the other components of the parallel reactor system. The injection needle continues to lower to supply material as described below. Once the fluid pressure is reduced, the injector is sealed which prevents the reflux of the fluid.

Reference is made to a third embodiment of the sealing element as 3c in Figure 8. The upper plate assembly 13 may include an O-ring 3c seated in the openings within the upper plate assembly. To supply material in the reaction vessel 9, the injection needle is lowered through the O-ring 3c thus forming an air tight seal with the O-ring 3c. The injection needle continues to lower to supply material as described below. In another embodiment, the sealing element 3 may be a valve (not shown).

In addition to the sealing element 3, the upper plate assembly 13 may include antechambers 2 (Figures 2-7) disposed above each reaction vessel 9. The antechambers 2 include inert gas inlets and ventilation outlets (not shown) to purge the antechamber. Corrosive gases may enter the antechamber 2 during the descent of the needle 50 into the reaction vessel 9 (Figures 6-7). The antechamber 2 allows said gases to be isolated and eliminated (and treated downstream) preventing said gases from coming into contact with other parts of the parallel reactor system.

In addition to the antechamber 2, the upper plate assembly 13 may include a port valve 5 (Figures 5-7) that isolates the antechamber 2 from the reaction vessel 9 when closed. The access valve 5 can be controlled by a drive mechanism 1. The access valve 5 can be closed while the injection needle 50 is lowered to engage the sealing element 3 and enter the antechamber 2. Inert gas can be introduced into the antechamber 2 and removed (optionally while creating a vacuum) to purge the antechamber of any fluid that is present in the needle. A gas manifold pressure system (not shown) attached to the arm of the dispensing system can be sealed with a hole 4 to apply a vacuum and / or apply an inert gas to the antechamber 2.

After purging the antechamber 2, the access valve 5 is opened and the needle 50 is lowered into the reaction chamber 9 (Figure 7) to supply material in the reaction chamber. In embodiments where the reaction vessel 9 is at a pressure different from the ambient pressure, the antechamber 2 is pressurized (or vacuum is applied) to substantially coincide with the pressure of the reaction chamber 9.

After supplying material through the injection needle 50 into the reaction vessel, the injection needle is raised until the tip of the injection passes through the port valve 5 to the antechamber 2. The port valve 5 it is closed and the liquid remaining in the needle is quickly directed backwards behind the first valve 71 of the dispensing system 15 (figure 12), for example, by means of a pump. The antechamber 2 is then purged with inert gas and brought to ambient pressure to purge any vapor that may be present in the needle 50. The injection needle 50 can be raised and removed after mounting 13 of the upper plate.

Referring now to Figure 12, an embodiment of a dispensing system 15 for use in the supply of two materials in each reaction vessel is shown. System 15 includes a first valve 71 used to control the flow of a first fluid (e.g., reaction fluid) through a first supply line 80 and a second valve 72 used to control the flow of a second fluid (by example, solvent) through a second supply line 76. The first fluid is generally different from the second fluid. The valves can be

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electronically or pneumatically operated. Allowing two fluids to be dosed through the use of a delivery system reduces cross contamination (and the resulting corrosion) by isolating the corrosive fluid from the surrounding atmosphere and providing a mechanism for the supply system to be rinsed with an inert material.

Other embodiments of the dispensing system use additional selection style valve (s) beyond those shown in Figure 12. This allows controlled volumes of different fluids to be contained within a single line and separated by air spaces. In this manner, the exact amount of corrosive fluid required may be contained behind the fluid valve described in Figure 12, followed by an air gap and a non-corrosive solvent type fluid. Upon delivery, the fluid valve is operated and sufficient volume is supplied to completely expel the corrosive fluid and a small portion of the air gap. After the fluid has been supplied completely, there is no massive amount of corrosive liquid that remains exposed to the surrounding atmosphere.

The parallel reactor system 10 (Figure 1) may include waste containers for the disposal of unreacted reagents or reaction by-products and other corrosive materials. In some embodiments and as shown in Figures 13-15, each waste container may be connected to a sealing assembly to prevent the material from being refilled from the waste container. The sealing assembly of the waste container includes a sealing element 84 and a valve 77. The sealing element 84 can be, for example, an O-ring that adapts to the size and shape of the supply needle 75 or the element The seal may be a septum or duckbill injector as described above in relation to the sealing element 3 (Figure 8) of the reactor matrix 20 (Figure 2). The reactor system may include two or more of said waste containers to avoid mixing two different waste streams that are capable of reacting strongly when combined. The flow switching between the waste containers can be achieved by means of a selector valve (not shown) that can be operated by software control, in accordance with the chemistry steps to avoid mixing incompatible waste streams.

To inject waste into the waste container, the waste supply needle 75 is placed through the sealing element 84 to form a primary seal. The valve 77 opens and the needle 75 descends through the valve 77. Fluid is injected into the waste container and the supply needle 75 is removed from the sealing element 84. The valve 77 is closed before the supply needle is removed from the sealed element to prevent material refilling of the waste containers.

The sealing system may include a port 81 to introduce inert gas into the waste container. An inert purge gas can be continuously fed to the waste container to exclude the surrounding atmosphere and avoid unwanted reaction with that atmosphere. The gas can be treated (for example, in a neutralization bubbler) and vented (not shown). Neutralization bubbles allow visual verification that ventilation is occurring. The bubbler may include any liquid (eg oil) that can neutralize corrosive gases and / or hazardous gases. After treatment, the gases can be vented through a hood. In some embodiments, the atmosphere is continuously ventilating.

In some embodiments, the waste containers are placed outside the main chamber 19 (Figure 1). The lines between the waste bins and the main chamber 19 are a potential entry path for the surrounding atmosphere. One or more check valves and / or solenoid valves can be used to prevent the surrounding atmosphere from entering the main chamber 19. The waste can be removed from the reaction vessels by pressurizing the reaction vessel above the pressure of the waste container (for example, by an inert gas) to cause the waste to flow into the waste container and empty completely into the container of waste

The upper plate assembly 13 (Figure 2) can also be used to sample the contents of the reaction vessels 9 for content analysis. As shown in Figures 16-18, the reaction contents are sampled using a sampling system 52 that includes a sampling needle 60 having a tip, a sampling pump 64 and a sampling valve 62 disposed between the tip of the needle 60 and the pump 64. The sampling system 60 is typically automated. Pump 64 is in fluid communication with a backup solvent 66 (for example, any suitable aqueous or organic solvent, typically with relatively low viscosity (eg, less than about 10 cP)) that is used to aspirate the sample. Pump 64 may be any suitable pump such as a syringe pump that is operable by means of a drive system (not shown).

To sample the material inside the reaction vessel 9 (Figure 2), the sampling needle 60 is lowered into the antechamber 2 as shown in Figure 17 to form a substantially fluid tight seal with the sealing element 3 of the antechamber When the port valve 5 is closed, the fluid is purged from the antechamber 2 by circulating inert gas through the antechamber. The pressure between antechamber 2 and reaction vessel 9 (Figure 2) is equalized (typically pressurizing the antechamber). In this regard, the present disclosure is not limited to a particular pressure. Pressures of up to approximately 3,500 kPa (approximately 507 psi) or more can be used without limitation. Alternatively, the reaction vessel 9 may be under vacuum.

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The reaction vessel may be referred to herein as "non-atmospheric" which is intended to include embodiments in which the reaction vessel is pressurized or embodiments in which the reaction vessel is under vacuum.

The atmosphere of the reaction vessel 9 may include an inert gas. By purging fluid from the antechamber 2 by circulating inert gas through the antechamber, an atmosphere of inert gas can be maintained in the reaction vessel 9 during and after sampling (i.e., the reaction vessel includes an inert atmosphere before lowering the sampling needle to the antechamber and the inert atmosphere is maintained at least until the port valve closes as described below).

Typically, the sampling needle 60 is filled with backing solvent (at the top of the needle) when the tip is lowered to the antechamber 2. In embodiments in which the antechamber 2 is pressurized, the pressurization of the antechamber 2 causes a quantity of steam to enter the sampling needle 60. This vapor separates the backing solvent from the sampled material during aspiration.

After adjusting the pressure of the antechamber 2 so that the pressure of the antechamber 2 is substantially the same as that of the reaction vessel 9, the access valve 5 opens and the sampling needle 60 is lowered into the reaction vessel as shown in figure 18. The sampling pump 64 works to reduce the pressure in the pump. The differential pressure causes a quantity of material (which can be referred to herein as the "sampling" bit of material) in the reaction vessel to enter the sampling needle 60. This volume of material can be referred to here as the sampling volume ”.

The sampling needle 60 containing the sample bar is then raised so that the tip of the sampling needle 60 is placed in the antechamber 2. The access valve 5 is closed after placing the tip in the antechamber 2. The Pump 64 is operated so that the bullet is further retracted into the sampling needle and / or sample lines. The sample is retracted until a first portion (e.g., upstream portion) of the bar is disposed between sampling valve 62 and sampling pump 64 and a second portion (e.g. downstream portion) is disposed between sampling valve 62 and needle tip 60 sampling. The amount of return solvent retracted by the pump 64 to retract the bar to the target position can be referred to herein as the "retraction volume". By not retracting the entire sample volume beyond the sampling valve 62, the gas does not retract beyond the sampling valve. Said gas can interfere with the accuracy and precision of the distributed sample volumes (for example, it can prevent the sample bar from moving during the depressurization stage described below). Said gas can displace the bar at random in the line that prevents the bar from dispensing in its entirety without supplying part of the return solvent. Supplying the solvent from the back distorts the composition of the sample and the concentration with respect to the content of the reaction vessel.

In some embodiments of the present description, the downstream part of the bar disposed between the sampling valve 62 and the tip of the sampling needle 60 is small enough for the downstream portion of the bar to remain in the needle 60 by surface tension.

After the bar is further retracted, the pressure in the antechamber 2 is adjusted to equalize the pressure in the housing 8 (Figure 1) in which the reactor matrix 20 is mounted. Typically, the reaction vessel 9 is pressurized relative to the housing so that the antechamber 2 is depressurized before removing the sampling needle 60 from the antechamber 2. By adjusting the pressure after the bar is further retracted, it can be prevent the supply of a portion of the bar in the reaction chamber. The steam can be purged from the antechamber 2 after the port valve is closed by circulating inert gas through the antechamber 2.

After adjusting the pressure in the antechamber 2, the sampling needle 60 can be removed from the antechamber 2 (ie, raising the sampling needle so that the sampling needle disengages the sealing element of the antechamber 3). Sampling needle 60 may be repositioned to an objective substrate (placed on or within said substrate) such as an analysis vessel such as HPLC vials, microtiter plates and the like or an analytical device such as HPLC, gas chromatography unit . In some embodiments, the target substrate is another reaction vessel such as in cases where the first reaction vessel is a reagent or catalyst that is used in the second vessel for an additional reaction. In this regard, the term "sampling" as used herein includes any method in which the material is removed from a reaction vessel for later use that includes further processing or analysis, unless otherwise indicated. The term "sampling" should not be considered in a limiting sense.

Once the sampling needle is repositioned, the pump 64 is operated to depressurize the material upstream of the tip valve 62. This depressurization causes the gas disposed between the sample bar and the backing solvent to expand. This increase in volume can be referred to here as the "depressurization volume". The sampling valve 62 opens and the pump 64 is operated to supply the sampling bar. In addition to the sample volume itself, the retraction volume is supplied to move at least the sample volume. A portion of the depressurization volume can also be supplied to ensure that the entire sample is supplied without administering solvent.

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The shrinkage volume and depressurization volumes described above can be determined by empirical methods. The precise volume will depend on the dynamics of the system, including the dimensioning of the injection needle and the associated connection lines, the return solvent, the sampled material and the pressure of the reaction vessel. The shrinkage volume can generally increase with increasing reactor pressure due to mechanical compliance in the sampling lines. The volume of depressurization (that is, the volume needed to hold the sample in the sampling system without the sample retracting or moving towards the tip when opening the sampling valve) can be determined by aspirating a sample volume (optionally with dye added to indicate the sample in transparent lines), depressurize a known volume and determine if the sample moves downstream or upstream after the sampling valve 62 is opened. The depressurization volume can be adjusted until the sample does not move upstream or downstream when the sampling valve 62 is opened.

The parallel reactor system 10 (Figure 1) may include several arms for injecting reagent and / or sampling reaction vessel, for example, automatically injecting reagent or taking samples, and may include additional reaction vessels, reagent storage and the like. The parallel reactor system may include various support elements to secure the system components and these support elements may be different from each other (similar to the housing sections) or may be integrally connected to the system. The system may employ various heating and / or cooling elements to heat and / or cool the reagents and / or reaction mixtures. In general, these components can be designed and selected according to the principles and standards within the high-performance parallel processing field. The various components may be linked to a controller (for example, a microcontroller or computer that includes computer software) that is configured to automatically operate the reactors in parallel, as those skilled in the art will understand.

The methods of the present disclosure for sampling reaction vessels of parallel reactor systems have several advantages compared to conventional methods. In embodiments in which the entire sample volume does not retract beyond the sampling valve 62, the gas is prevented from retracting beyond the sampling valve. Such gas interferes with the accuracy and precision of the sample volumes supplied. In addition, for given system hardware (for example, given size tube and sampling needle), the methods allow a relatively small sample volume to be sampled while the sample is depressurized in a controllable manner. Such sample volumes may vary from about 25 to about 100 microliters or even as low as 5 microliters. By purging the antechamber with an inert gas during sampling, an inert gas, an inert gas atmosphere can be maintained in the reaction vessel 9 during and after sampling. In addition, the parallel reactor system 10 described above can be used with reagents that are corrosive, and / or to produce reaction products that are corrosive. The sampling protocol can prevent uncontrolled release of corrosive material from the sampling needle (for example, release into other components of the reactor system that can cause corrosion). The reactor system can be configured to reduce the amount of corrosive material that can escape the storage of the reagent or reaction vessel during or after the injection of the corrosive material. For the purposes of the present disclosure, the term "corrosive" includes materials that cause oxidation or other weakening of the common components of the reactor system that cause the components to have to be replaced before their expected useful life. Such corrosive materials include materials that in turn are corrosive and / or that can react with environmental materials such as water vapor or oxygen or can react with other reaction reagents to create a corrosive material.

When elements of the present description or the embodiment (s) thereof are introduced, the articles "a", "one", "the" and "said" are intended to indicate that there are one or more of the elements. The terms "comprising", "including", "containing" and "having" are intended to be inclusive and means that there may be additional elements other than the elements listed. The use of terms that indicate a particular orientation (for example, "upper", "lower", "lateral", etc.) is for the convenience of the description and does not require any particular orientation of the described element.

As several changes could be made to the previous constructions and methods without departing from the scope of the disclosure, it is intended that all the material contained in the above description and shown in the attached drawing (s) will be interpreted as illustrative and not in a limiting sense .

Claims (14)

5 10 fifteen twenty 25 30 35 40 Four. Five fifty 55 60 65 1. A method for sampling from a non-atmospheric reaction vessel of a parallel reactor system, the reactor system includes a reactor assembly comprising at least two reaction vessels, antechambers arranged above each reaction vessel, sealing elements of the antechamber, a port valve disposed between each antechamber and each reaction vessel and a sampling system for sampling material from the reaction vessels, the sampling system comprises a sampling pump, a sampling needle has a tip and a valve sampling method arranged between the sampling pump and the tip, the method comprises: lower the sampling needle to an antechamber to form a substantially fluid tight seal between the seal member of the anteroom and the sampling needle; lower the sampling needle in the reaction vessel, the vessel has reactor material therein; introducing material from the reaction vessel into the sampling needle to form a sample fuel rod; lift the sampling needle to place the tip of the sampling needle in the antechamber; close the port valve after placing the tip of the sampling needle in the antechamber; retract the bar so that a first portion is disposed between the sampling valve and the sampling pump and a second portion is disposed between the sampling valve and the tip of the sampling needle; Y unload the bar on a target substrate. 2. The method as set forth in claim 1, further comprising depressurizing the antechamber after retracting the bar. 3. The method as set forth in claim 1 or claim 2, wherein the second portion of material disposed between the sampling valve and the tip of the sampling needle when retracting the rod is suspended in the sampling system by surface tension. 4. The method as set forth in any one of claims 1 to 3 wherein the reactor assembly comprises 2 reaction vessels or more or 4 reaction vessels or more, 8 reaction vessels or more, 16 reaction vessels or more or 48 reaction vessels or more. 5. The method as set forth in any one of claims 1 to 4, further comprising equalizing the pressure between the antechamber and the reaction vessel after lowering the sampling needle towards the antechamber and before lowering the sampling needle towards the reaction vessel 6. The method as set forth in claim 5, wherein the antechamber is pressurized. 7. The method as set forth in any one of claims 1 to 6 further comprising purging the fluid from the antechamber after lowering the sampling needle in the antechamber and before lowering the sampling needle in the reaction vessel. 8. The method as set forth in any one of claims 1 to 7, wherein the discharge of the bar into an objective substrate comprises: open the sample valve; Y Operate the pump to allow the material to discharge onto an objective substrate. 9. The method as set forth in any one of claims 1 to 8, wherein the target substrate is an analysis vessel, analytical device or second reaction vessel. 10. The method as set forth in any one of claims 1 to 9, further comprising purging steam from the antechamber after the port valve is closed. 11. The method as set forth in any one of claims 1 to 10, further comprising opening the port valve after lowering the sampling needle in the antechamber and before lowering the sampling needle in the reaction vessel. 12. The method as set forth in any one of claims 1 to 11, wherein downloading the bar into an objective substrate comprises: raise the sampling needle so that the tip of the sampling needle disengages the sealing element from the antechamber; Y position the sampling needle on the target substrate. The method as set forth in any one of claims 1 to 12, wherein the pressure in the container Reaction is higher than atmospheric pressure. 14. The method as set forth in any one of claims 1 to 13, wherein the pressure in the reaction vessel is below atmospheric pressure. 10 15. The method as set forth in any one of claims 1 to 14, wherein the pump is a syringe pump.